DE112006003401T5 - Cationic compositions of electrically conductive polymers doped with fully fluorinated acid polymers - Google Patents

Abstract

An electrically conductive polymer composition comprising an electrically conductive polymer and a fully fluorinated acid polymer having acidic anion groups, wherein a first portion of the acidic anion groups is complexed with the electrically conductive polymer and a second portion of the acidic anionic groups in the form of a salt with cations selected from inorganic cations , organic cations and combinations thereof, wherein the cation concentration is in the range of 5 x 10 ^-5 to 0.2 moles of cation per gram of solids, the solids consisting essentially of the total of the electrically conductive polymer plus the fully fluorinated acidic polymer ,

Description

CROSS-REFERENCE TO RELATED REGISTRATIONS

These Registration claims priority over the provisional one US Application 60/754338, filed on Dec. 28, 2005, which incorporated herein by reference as if complete would be indicated.

BACKGROUND INFORMATION

AREA OF REVELATION

These The invention generally relates to electrically conductive Polymer compositions and their use in organic electronic Devices.

DESCRIPTION OF THE RELATED TECHNIQUE

organic electronic devices define a category of products, which include an active layer. Such devices convert electrical energy into radiation, transmit signals electronic processes, convert radiation into electrical energy surround or close one or more organic semiconductor layers one.

organic Light Emitting Diodes (OLEDs) are organic electronic devices, comprising an organic electroluminescent capable Layer. OLEDs can have the following configuration:

Anode / buffer layer / EL material / cathode

The Anode is typically a material that is transparent and that Ability to inject holes into the EL material, such as indium / tin oxide (ITO). The anode is optional supported on a glass or plastic substrate. To EL materials include fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers and mixtures from that. The cathode is typically a material (such as Ca or Ba), which has the ability to transfer electrons into the EL material inject. The buffer layer is typically an electrical one conductive polymer and facilitates the injection of holes from the anode to the EL material layer. The buffer layer can also have other properties that the performance of the Facilitate device.

It There is a continuing need for buffer materials improved properties.

SUMMARY

There is provided an electrically conductive polymer composition comprising an electrically conductive polymer and a fully fluorinated acid polymer having acidic anionic groups, wherein a first portion of the acidic anionic groups is complexed with the electrically conductive polymer and a second portion of the acidic anionic groups in the form of a salt with cations, selected from inorganic cations, organic cations, and combinations thereof, wherein the cation concentration is in the range of 5 x 10 ^-5 to 0.2 moles of cation per gram of solids, the solids consisting essentially of the total of the electrically-conductive polymer plus the fully fluorinated acid polymer.

In another embodiment, an aqueous dispersion of an electrically conductive polymer and a fully fluorinated acid polymer having acidic anion groups is provided, wherein a first portion of the acidic anionic groups is complexed with the electrically conductive polymer and a second portion of the acidic anionic groups in the form of a salt with cations which is selected from inorganic cations, organic cations, and combinations thereof, wherein the cation concentration is in the range of 5 x 10 ^-5 to 0.2 moles of cation per gram of solids, the solids consisting essentially of the total of the electrically-conductive polymer plus the fully fluorinated acid polymer.

In In another embodiment, electronic devices, comprising at least one layer comprising the new conductive Polymer composition provided.

The foregoing general description and the following detailed description are unanswered It is by way of example and by way of illustration and not limitation of the invention as defined in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The Embodiments are illustrated in the accompanying figures, to understand concepts as presented here be, improve.

1 includes a diagram illustrating the contact angle.

2 includes a schematic diagram of an electronic device.

Of the One skilled in the art recognizes that objects in the figures illustrated for simplicity and clarity and not necessarily drawn in scale. For example can change the dimensions of some of the items exaggerated in the figures relative to other objects be to help understanding the embodiments to improve.

DETAILED DESCRIPTION

Lots Aspects and embodiments are described above and are merely exemplary and not limiting. To The skilled person will recognize from reading this description that others Aspects and embodiments are possible without deviate from the scope of the invention.

Other Features and advantages of one or more of the embodiments are from the following detailed description and out the claims obvious. The detailed Description first addresses the definitions and the clarification of terms, subsequently the conductive one Polymer, the fully fluorinated acid polymer, the cations, the preparation of the doped electrically conductive polymer composition, the replacement of acidic protons with cations, the electronic ones Devices and finally the examples too.

1. DEFINITIONS AND CLARIFICATION OF TERMS, USED IN THE DESCRIPTION AND CLAIMS

Before we will get details of embodiments described below turn some terms are defined or clarified.

As used herein, the term "conductor" and its variants are intended to mean a layered material, component or structure having an electrical property such that current flows through a layered material, component or structure without any substantial drop in potential is intended to include semiconductors In one embodiment, a conductor forms a layer having a conductivity of at least 10 ^-7 S / cm.

Of the Term "electrically conductive material" a material which without the addition of carbon black or conductive Metal particles inherent or intrinsic to electrical Conductivity is capable.

Of the Term "buffer layer" or "buffer material" should be electrically conductive or semiconductive Materials can mean one or more functions in one have organic electronic device, to which, but without to be limited to, planarization of the underlying layer, Charge transport and / or charge injection properties, trapping impurities such as oxygen or metal ions and other aspects belong to the operating behavior of the facilitate or improve organic electronic device. Buffer materials may be polymers, oligomers or small ones Be molecules and can be in the form of solutions, Dispersions, suspensions, emulsions, colloidal mixtures or other compositions.

"Hole transport" should, when referring to a layer, a material, a component or a structure, such a layer, a material, a Ingredient or structure that means the migration of positive Charges through the thickness of such a layer, a material, a constituent or structure with relative effectiveness and low loss of charge. As used here does not include the term "hole transport layer" a light emitting layer, even if this layer has some hole transporting properties may have.

Of the Term "polymer" is intended to mean a material having at least one mean repetitive monomeric unit. The term concludes Homopolymers of only one kind, or species, of monomeric unit and copolymers having two or more different monomers Units, including copolymers, produced from monomers Units of different species, one.

Of the Term "fully fluorinated acid polymer" a polymer with acidic groups, where all the available Hydrogen atoms bound to carbon have been replaced by fluorine are.

Of the Term "acidic group" refers to a group that is capable for ionizing, wherein a hydrogen ion to a Brønsted base is delivered.

Of the The term "acid anion group" refers to the anionic Group that remains when a hydrogen ion from an acidic Group is removed.

The Composition can be one or more different electrically conductive polymers and one or more different ones fully fluorinated acid polymers.

Of the The term "doped" is intended to refer to an electric refers conductive polymer, mean that the electric conductive polymer has a polymeric counterion to the charge to balance on the conductive polymer.

Of the Term "doped conductive polymer" is the conductive polymer and the polymeric counterion that works with it is connected mean.

As used herein are the terms "comprises", "comprising", "closes a "," including "," has "," with " or any other variation thereof, a non-exclusive one Cover enclosure. For example, a method, a Method, an item or an apparatus that has a list of Elements, not necessarily only on these Limited to elements but may include other elements not expressly listed or inherent for such a method, a method, an object or an apparatus. Further, if not expressly designated to the contrary stated, "or" an inclusive or and not an exclusive or. For example condition A or B is fulfilled by each of the following: A is correct (or exists) and B is false (or absent), A is wrong (or not present) and B is correct (or exists) and both A and B are correct (or present).

Furthermore is the use of "a" or "one" applied, to describe elements and components described here. This is done simply for the sake of convenience and for a general feeling to give the scope of the invention. This description should read be to include one or at least one and the singular also includes the plural, if it is not it is obvious that it is meant otherwise.

The group numbers corresponding to the columns within the periodic system of elements use the convention of "New Notation" as they are described in the CRC Handbook of Chemistry and Physics, 81st Edition (81st Edition) (2000-2001) is seen.

If not otherwise defined have all technical used here and scientific terms have the same meaning as they usually do one skilled in the art to which the invention belongs, is understood. Although procedures and materials similar or equivalent to those described here in the practice or testing of the embodiments can be used in the present invention Below, suitable methods and materials are described. All Publications, patent applications, patents and other references mentioned here are by Reference incorporated in its entirety, if not a special one Passage is cited. In the case of conflict, the present Determine the description including the definitions. Moreover, the materials, methods and examples are merely illustrative and not intended to be limiting.

In to the extent not described here are many details regarding special materials, procedures and circuits conventional and can in textbooks and other sources within the subject areas from display organic light emitting diode, illumination source, Photodetector, photovoltaic and semiconducting component being found.

2. CONDUCTIVE POLYMER

In one embodiment, the conductive polymer forms a film having a conductivity of at least 10 ^-7 S / cm. The monomer from which the conductive polymer is made is referred to as a "precursor monomer." A copolymer will have more than one precursor monomer.

In One embodiment is the conductive polymer from at least one precursor monomer selected from thiophenes, selenophenes, tellurophenes, pyrroles, anilines and polycyclic aromatics. The polymers that are made These monomers are prepared here as polythiophenes, Poly (selenophene), poly (tellurophene), polypyrrole, polyaniline or polycyclic aromatic polymers. The term "polycyclic aromatic "means compounds with more than one aromatic Ring. The rings can be linked by one or more bonds be connected, or they may be condensed together. The term "aromatic ring" is intended to be heteroaromatic Include rings. A "polycyclic heteroaromatic" Compound has at least one heteroaromatic ring. In a Embodiment are the polycyclic aromatic polymers Poly (thienothiophenes).

wobei:
Q aus der Gruppe, bestehend aus S, Se und Te, ausgewählt ist;
R¹ unabhängig ausgewählt ist, um bei jedem Vorkommen gleich oder verschieden zu sein und aus Wasserstoff, Alkyl, Alkenyl, Alkoxy, Alkanoyl, Alkylthio, Aryloxy, Alkylthioalkyl, Alkylaryl, Arylalkyl, Amino, Alkylamino, Dialkylamino, Aryl, Alkylsulfinyl, Alkoxyalkyl, Alkylsulfonyl, Arylthio, Arylsulfinyl, Alkoxycarbonyl, Arylsulfonyl, Acrylsäure, Phosphorsäure, Phosphonsäure, Halogen, Nitro, Cyano, Hydroxyl, Epoxy, Silan, Siloxan, Alkohol, Benzyl, Carboxylat, Ether, Ethercarboxylat, Amidosulfonat, Ethersulfonat, Estersulfonat und Urethan ausgewählt ist; oder beide R¹-Gruppen zusammen eine Alkylen- oder Alkenylenkette bilden können, die einen 3-, 4-, 5-, 6- oder 7-gliedrigen aromatischen oder alicyclischen Ring vervollständigt, welcher Ring gegebenenfalls ein oder mehrere zweiwertige Stickstoff-, Selen-, Tellur-, Schwefel- oder Sauerstoffatome einschließen kann.In one embodiment, monomers contemplated for use to produce the electrically conductive polymer in the novel composition include Formula I below:

in which:
Q is selected from the group consisting of S, Se and Te;
R ^{1 is} independently selected to be the same or different at each occurrence and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl , Arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ethercarboxylate, amidosulfonate, ether sulfonate, ester sulfonate and urethane; or both R ¹ groups may together form an alkylene or alkenylene chain which completes a 3-, 4-, 5-, 6- or 7-membered aromatic or alicyclic ring, which ring optionally contains one or more divalent nitrogen, selenium , Tellurium, sulfur or oxygen atoms.

As As used herein, the term "alkyl" refers to a group derived from an aliphatic hydrocarbon, and includes linear, branched and cyclic groups which are unsubstituted or substituted. The term "heteroalkyl" is intended to mean an alkyl group wherein one or more of the carbon atoms within the alkyl group by another atom, such as Nitrogen sulfur and the like have been replaced. The term "alkylene" denotes an alkyl group having two attachment sites.

As As used herein, the term "alkenyl" refers to a group derived from an aliphatic hydrocarbon with at least a carbon-carbon double bond, and concludes linear, branched and cyclic groups which are unsubstituted or substituted. The term "heteroalkenyl" is intended to mean an alkenyl group, with one or more of the Carbon atoms within the alkenyl group by another Atom, such as nitrogen, oxygen, sulfur and the like, have been replaced. The term "alkenylene" denotes an alkenyl group with two attachment sites.

As used herein, the following terms for substituent groups denote the formulas given below: "Alcohol" -R ³ -OH "Amido" -R ³ -C (O) N (R ⁶ ) R ⁶ "Amidosulfonate" -R ³ -C (O) N (R ⁶ ) R ⁴ -SO ₃ Z "Benzyl" -CH ₂ -C ₆ H ₅ "Carboxylate" -R ³ -C (O) OZ or -R ³ -OC (O) -Z "Ether" -R ³ - (OR ⁵ ) _p -OR ⁵ "Ether carboxylate" -R ³ -OR ⁴ -C (O) OZ or -R ³ -OR ⁴ -OC (O) -Z "Ether sulfonate" -R ³ -OR ⁴ -SO ₃ Z "Ester sulfonate" -R ³ -OC (O) -R ⁴ -SO ₃ Z "Sulfonimide" -R ³ -SO ₂ -NH-SO ₂ -R ⁵ "Urethane" -R ³ -OC (O) -N (R ⁶ ) ₂ where all "R" groups are the same or different at each occurrence, and
R ^{3 is} a single bond or an alkylene group
R ^{4 is} an alkylene group
R ^{5 is} an alkyl group
R ^{6 is} hydrogen or an alkyl group
p is 0 or an integer from 1 to 20
Z is H, alkali metal, alkaline earth metal, N (R ⁵ ) ₄ or R ⁵

each the above groups may be further unsubstituted or substituted and each group can be F for one or more hydrogen atoms substituted, including perfluorinated groups. In one embodiment, the alkyl and alkylene groups from 1-20 carbon atoms.

In one embodiment, in the monomer both R ¹ together form -O- (CHY) _m -O-, where m is 2 or 3 and Y is the same or different at each occurrence and selected from hydrogen, alkyl, alcohol, amidosulfonate, benzyl, carboxylate, Ether, ether carboxylate, ether sulfonate, ester sulfonate and urethane is selected where the Y groups may be partially or fully fluorinated. In one embodiment, all Y are hydrogen. In one embodiment, the polymer is poly (3,4-ethylenedioxythiophene). In one embodiment, at least one Y group is not hydrogen. In one embodiment, at least one Y group is a substituent with F substituted for at least one hydrogen. In one embodiment, at least one Y group is perfluorinated.

wobei:
Q aus der Gruppe bestehend aus S, Se, und Te, ausgewählt ist;
R⁷ bei jedem Vorkommen gleich oder verschieden ist und aus Wasserstoff Heteroalkyl, Alkenyl, Heteroalkenyl, Alkohol, Amidosulfonat, Benzyl, Carboxylat, Ether, Ethercarboxylat, Ethersulfonat, Estersulfonat und Urethan ausgewählt ist, mit der Maßgabe, daß mindestens ein R⁷ nicht Wasserstoff ist, und
m 2 oder 3 ist.In one embodiment, the monomer has Formula I (a):

in which:
Q is selected from the group consisting of S, Se, and Te;
R ^{7 is the} same or different at each occurrence and is selected from hydrogen heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate and urethane, provided that at least one R ^{7 is} not hydrogen , and
m is 2 or 3.

In one embodiment of Formula I (a), m is two, one R ^{7 is} an alkyl group of more than 5 carbon atoms and all the others R ^{7 are} hydrogen. In one embodiment of formula I (a), at least one R ⁷ group is fluorinated. In one embodiment, at least one R ⁷ group has at least one fluorine substituent. In one embodiment, the R ⁷ group is fully fluorinated

In one embodiment of Formula I (a), the R ⁷ substituents on the fused alicyclic ring on the monomer provide improved solubility of the monomers in water and facilitate polymerization sation in the presence of the fluorinated acid polymer.

In one embodiment of formula I (a), m is 2, one R ^{7 is} sulfonic acid propylene ether methylene and all other R ^{7 are} hydrogen. In one embodiment, m is 2, one R ⁷ is propyl-ether-ethylene and all other R ⁷ is hydrogen. In one embodiment, m is 2, one R ^{7 is} methoxy and all others R ^{7 are} hydrogen. In one embodiment, one R ^{7 is} sulfonic acid difluoromethylenestermethylene (-CH ₂ -OC (O) -CF ₂ -SO ₃ H) and all other R ^{7 are} hydrogen.

wo in Formel II:
R¹ unabhängig ausgewählt ist, um bei jedem Vorkommen gleich oder verschieden zu sein und aus Wasserstoff, Alkyl, Alkenyl, Alkoxy, Alkanoyl, Alkylthio, Aryloxy, Alkylthioalkyl, Alkylaryl, Arylalkyl, Amino, Alkylamino, Dialkylamino, Aryl, Alkylsulfinyl, Alkoxyalkyl, Alkylsulfonyl, Arylthio, Arylsulfinyl, Alkoxycarbonyl, Arylsulfonyl, Acrylsäure, Phosphorsäure, Phosphonsäure, Halogen, Nitro, Cyano, Hydroxyl, Epoxy, Silan, Siloxan, Alkohol, Benzyl, Carboxylat, Ether, Amidosulfonat, Ethercarboxylat, Ethersulfonat, Estersulfonat und Urethan ausgewählt ist; oder beide R¹-Gruppen zusammen eine Alkylen- oder Alkenylenkette bilden können, die einen 3-, 4-, 5-, 6- oder 7-gliedrigen aromatischen oder alicyclischen Ring vervollständigt, welcher Ring gegebenenfalls ein oder mehrere zweiwertige Stickstoff-, Schwefel-, Selen-, Tellur-, oder Sauerstoffatome einschließen kann; und
R² unabhängig ausgewählt ist, um bei jedem Vorkommen gleich oder verschieden zu sein und aus Wasserstoff Alkenyl, Aryl, Alkanoyl, Alkylthioalkyl, Alkylaryl, Arylalkyl, Amino, Epoxy, Silan, Siloxan, Alkohol, Benzyl, Carboxylat, Ether, Ethercarboxylat, Ethersulfonat, Estersulfonat und Urethan ausgewählt ist.In one embodiment, pyrrole monomers contemplated for use to produce the electrically conductive polymer in the novel composition include Formula II below.

where in formula II:
R ^{1 is} independently selected to be the same or different at each occurrence and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl , Arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, amidosulfonate, ethercarboxylate, ether sulfonate, ester sulfonate and urethane; or both R ¹ groups may together form an alkylene or alkenylene chain which completes a 3-, 4-, 5-, 6- or 7-membered aromatic or alicyclic ring, which ring optionally contains one or more divalent nitrogen, sulfur , May include selenium, tellurium, or oxygen atoms; and
R ^{2 is} independently selected to be the same or different at each occurrence and selected from hydrogen alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ethercarboxylate, ether sulfonate, Estersulfonat and urethane is selected.

In one embodiment, R ^{1 is the} same or different at each occurrence and is independently selected from hydrogen, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alcohol, benzyl, carboxylate, ether, amidosulfonate, ether carboxylate, ether sulfonate, ester sulfonate, urethane, epoxy, silane, Siloxane and alkyl substituted with one or more of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane or siloxane units.

In one embodiment, R ^{2 is selected} from hydrogen, alkyl and alkyl substituted with one or more of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, cyano, hydroxyl, epoxy, silane or siloxane units.

In one embodiment, the pyrrole monomer is re-substituted and both R ¹ and R ^{2 are} hydrogen.

In one embodiment, both R ¹ together form a 6- or 7-membered alicyclic ring which is further substituted with a group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate and urethane. These groups can improve the solubility of the monomer and the resulting polymer. In one embodiment, both R ¹ together form a 6- or 7-membered alicyclic ring further substituted with an alkyl group. In one embodiment, both R ¹ together form a 6- or 7-membered alicyclic ring further substituted with an alkyl group of at least 1 carbon atom.

In one embodiment, both R ¹ together form -O- (CHY) _m -O-, where m is 2 or 3 and Y is the same or different at each occurrence, and from hydrogen alkyl, alcohol, benzyl, carboxylate, amidosulfonate, ether, ether carboxylate , Ether sulfonate, ester sulfonate and urethane is selected. In one embodiment, at least one Y group is not hydrogen. In one embodiment, at least one Y group is a substituent with F substituted for at least one hydrogen. In one embodiment, at least one Y group is perfluorinated.

wobei:
a 0 oder eine ganze Zahl von 1 bis 4 ist;
b eine ganze Zahl von 1 bis 5 ist, mit der Maßgabe, daß a + b = 5; und
R¹ unabhängig ausgewählt ist, um bei jedem Vorkommen gleich oder verschieden zu sein und aus Wasserstoff, Alkyl, Alkenyl, Alkoxy, Alkanoyl, Alkylthio, Aryloxy, Alkylthioalkyl, Alkylaryl, Arylalkyl, Amino, Alkylamino, Dialkylamino, Aryl, Alkylsulfinyl, Alkoxyalkyl, Alkylsulfonyl, Arylthio, Arylsulfinyl, Alkoxycarbonyl, Arylsulfonyl, Acrylsäure, Phosphorsäure, Phosphonsäure, Halogen, Nitro, Cyano, Hydroxyl, Epoxy, Silan, Siloxan, Alkohol, Benzyl, Carboxylat, Ether, Ethercarboxylat, Amidosulfonat, Ethersulfonat, Estersulfonat und Urethan ausgewählt ist; oder beide R¹-Gruppen zusammen eine Alkylen- oder Alkenylenkette bilden können, die einen 3-, 4-, 5-, 6- oder 7-gliedrigen aromatischen oder alicyclischen Ring vervollständigt, welcher Ring gegebenenfalls ein oder mehrere zweiwertige Stickstoff-, Schwefel- oder Sauerstoffatome einschließen kann.In one embodiment, aniline monomers contemplated for use to form the electrically conductive polymer in the novel composition include Formula III below.

in which:
a is 0 or an integer from 1 to 4;
b is an integer from 1 to 5, with the proviso that a + b = 5; and
R ^{1 is} independently selected to be the same or different at each occurrence and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl , Arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ethercarboxylate, amidosulfonate, ether sulfonate, ester sulfonate and urethane; or both R ¹ groups may together form an alkylene or alkenylene chain which completes a 3-, 4-, 5-, 6- or 7-membered aromatic or alicyclic ring, which ring optionally contains one or more divalent nitrogen, sulfur or oxygen atoms.

wo a, b und R¹ wie vorstehend definiert sind.When polymerized, the monomeric aniline moiety may have Formula IV (a) or Formula IV (b), shown below, or a combination of both formulas.

where a, b and R ^{1 are} as defined above.

In In one embodiment, the aniline monomer is unsubstituted and a = 0.

In one embodiment, a is not 0 and at least one R ^{1 is} fluorinated. In one embodiment, at least one R ^{1 is} perfluorinated.

wobei:
Q S, Se, Te oder NR⁶ ist;
R⁶ Wasserstoff oder Alkyl ist;
R⁸, R⁹, R¹⁰ und R¹¹ unabhängig ausgewählt sind, um bei jedem Vorkommen gleich oder verschieden zu sein, und aus Wasserstoff, Alkyl, Alkenyl, Alkoxy, Alkanoyl, Alkylthio, Aryloxy, Alkylthioalkyl, Alkylaryl, Arylalkyl, Amino, Alkylamino, Dialkylamino, Aryl, Alkylsulfinyl, Alkoxyalkyl, Alkylsulfonyl, Arylthio, Arylsulfinyl, Alkoxycarbonyl, Arylsulfonyl, Acrylsäure, Phosphorsäure, Phosphonsäure, Halogen, Nitro, Nitril, Cyano, Hydroxyl, Epoxy, Silan, Siloxan, Alkohol, Benzyl, Carboxylat, Ether, Ethercarboxylat, Amidosulfonat, Ethersulfonat, Estersulfonat und Urethan ausgewählt sind; und
mindestens eines von R⁸ und R⁹, R⁹ und R¹⁰, und R¹⁰ und R¹¹ zusammen eine Alkenylenkette bilden, die einen 5 oder 6-gliedrigen aromatischen Ring vervollständigt, welcher Ring gegebenenfalls ein oder mehrere zweiwertige Stickstoff-, Schwefel-, Selen-, Tellur- oder Sauerstoffatome einschließen kann.In one embodiment, fused polycyclic heteroaromatic monomers contemplated for use to make the electrically conductive polymer in the novel composition have two or more fused aromatic rings, at least one of which is heteroaromatic. In one embodiment, the fused polycyclic heteroaromatic monomer has Formula V:

in which:
Q is S, Se, Te or NR ⁶ ;
R ^{6 is} hydrogen or alkyl;
R ⁸ , R ⁹ , R ¹⁰ and R ^{11 are} independently selected to be the same or different at each occurrence, and selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino , Dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate , Amidosulfonate, ether sulfonate, ester sulfonate and urethane; and
at least one of R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹⁰ and R ¹¹ together form an alkenylene chain which completes a 5 or 6 membered aromatic ring, which ring optionally contains one or more divalent nitrogen, sulfur, Selenium, tellurium or oxygen atoms can include.

wobei:
Q S, Se, Te oder NH ist; und
T bei jedem Vorkommen gleich oder verschieden ist und aus S, NR⁶, O, SiR⁶ ₂, Se, Te und PR⁶ ausgewählt ist;
R⁶ Wasserstoff oder Alkyl ist.In one embodiment, the fused polycyclic heteroaromatic monomer has formula V (a), V (b), V (c), V (d), V (e), V (f) and V (g):

in which:
Q is S, Se, Te or NH; and
T is the same or different at each occurrence and is selected from S, NR ⁶ , O, SiR ⁶ ₂ , Se, Te and PR ⁶ ;
R ^{6 is} hydrogen or alkyl.

The condensed polycyclic heteroaromatic monomers can further with groups selected from alkyl, heteroalkyl, Alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, Ester sulfonate and urethane, be substituted. In one embodiment the substituent groups are fluorinated. In one embodiment the substituent groups are fully fluorinated.

In One embodiment is the condensed polycyclic heteroaromatic monomer a thieno (thiophene). Such compounds are in, for example, Macromolecules, 34, 5746-5747 (2001); and Macromolecules, 35, 7281-7286 (2002). In one embodiment, the thieno (thiophene) is thieno (2,3-b) thiophene, Thieno (3,2-b) thiophene and thieno (3,4-b) thiophene selected. In one embodiment, the thieno (thiophene) monomer further with at least one group selected from alkyl, Heteroalkyl, alcohol, benzyl, carboxylate, ether, ethercarboxylate, Ethersulfonat, ester sulfonate and urethane, substituted. In a Embodiment, the substituent groups are fluorinated. In one embodiment, the substituent groups are fully fluorinated.

wobei:
Q S, Se, Te oder NR⁶ ist;
T aus S, NR⁶, O, SiR⁶ ₂, Se, Te und PR⁶ ausgewählt ist;
E aus Alkenylen, Arylen und Heteroarylen ausgewählt ist;
R⁶ Wasserstoff oder Alkyl ist;
R¹² bei jedem Vorkommen gleich oder verschieden ist und aus Wasserstoff, Alkyl, Alkenyl, Alkoxy, Alkanoyl, Alkylthio, Aryloxy, Alkylthioalkyl, Alkylaryl, Arylalkyl, Amino, Alkylamino, Dialkylamino, Aryl, Alkylsulfinyl, Alkoxyalkyl, Alkylsulfonyl, Arylthio, Arylsulfinyl, Alkoxycarbonyl, Arylsulfonyl, Acrylsäure, Phosphorsäure, Phosphonsäure, Halogen, Nitro, Nitril, Cyano, Hydroxyl, Epoxy, Silan, Siloxan, Alkohol, Benzyl, Carboxylat, Ether, Ethercarboxylat, Amidosulfonat, Ethersulfonat, Estersulfonat und Urethan ausgewählt ist; oder beide R¹²-Gruppen zusammen eine Alkylen- oder Alkenylenkette bilden können, die einen 3-, 4-, 5-, 6- oder 7-gliedrigen aromatischen oder alicyclischen Ring vervollständigt, welcher Ring gegebenenfalls ein oder mehrere zweiwertige Stickstoff-, Schwefel-, Selen-, Tellur-, oder Sauerstoffatome einschließen kann.In one embodiment, polycyclic heteroaromatic monomers contemplated for use to produce the polymer in the novel composition include Formula VI:

in which:
Q is S, Se, Te or NR ⁶ ;
T is selected from S, NR ⁶ , O, SiR ⁶ ₂ , Se, Te and PR ⁶ ;
E is selected from alkenylene, arylene and heteroarylene;
R ^{6 is} hydrogen or alkyl;
R ^{12 is the} same or different at each occurrence and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl , Arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ethercarboxylate, amidosulfonate, ether sulfonate, ester sulfonate and urethane; or both R ¹² groups may together form an alkylene or alkenylene chain which completes a 3-, 4-, 5-, 6- or 7-membered aromatic or alicyclic ring, which ring optionally contains one or more divalent nitrogen, sulfur , Selenium, tellurium, or oxygen atoms.

In In one embodiment, the electrically conductive Polymer from the group consisting of thiophenes, pyrroles, thienothiophenes and mixtures thereof.

In In one embodiment, the electrically conductive Polymer is a copolymer of a precursor monomer and at least a second monomer. Any type of second monomer can be used as long as he does not adversely affect the desired Properties of the copolymer affected. In one embodiment the second monomer does not comprise more than 50% of the polymer, based on the total number of monomer units. In one embodiment the second monomer does not comprise more than 30%, based on the total number of monomer units. In one embodiment the second monomer does not comprise more than 10%, based on the total number of monomer units.

To Exemplary types of second monomers include, without but to be limited to alkenyl, alkynyl, arylene and heteroarylene. Examples of second monomers include, but not including to be limited to fluorene, oxadiazole, thiadiazole, benzothiadiazole, Phenylenevinylene, phenylenethynylene, pyridine, diazines and triazines, all of which may be further substituted.

In In one embodiment, the copolymers are prepared by first adding an intermediate precursor monomer with the structure A-B-C where A and C are precursor monomers represent which may be the same or different, and B represents a second monomer. The intermediate A-B-C precursor monomer Can be made using standard organic Synthesis techniques, such as Yamamoto, Stille, Grignard metathesis, Suzuki and Negishi couplings. The copolymer is then oxidative polymerization of the intermediate Precursor monomer alone or with one or more additional Produced precursor monomers.

In In one embodiment, the electrically conductive Polymer is a copolymer of two or more precursor monomers. In one embodiment, the precursor monomers are from a thiophene, a selenophene, a tellurophene, a pyrrole and a thienothiophene.

3. FULL-FLUORED ACID POLYMERS

The Fully fluorinated acid polymer ("FFAP") may be a be any polymer which is fully fluorinated and acidic groups with acidic protons. The acidic groups provide an ionizable Proton. In one embodiment, the acidic proton has one pKa less than 3. In one embodiment, the acidic proton has a pKa of less than 0. In one embodiment the acidic proton has a pKa of less than -5. The acidic group can be linked directly to the polymer backbone be, or it may have side chains on the polymer backbone be linked. Examples of acidic groups include but not limited to carboxylic acid groups, Sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups and combinations thereof. The acidic groups can all be the same, or the polymer can be more than one type of acidic Have group. In one embodiment, the acidic Groups from the group consisting of sulphonic acid groups, Sulfonimide groups and combinations thereof.

In The FFAP is a first fraction of the acidic groups in the form of be acidic anion groups and is with the electrically conductive Complexed polymer. This is the electrically conductive polymer doped with the FFAP. A second part of the acid groups of the FFAP is selected in the form of a salt with cations from inorganic cations, organic cations and combinations from that. In some cases, a third share of the acidic groups in the protonated, acidic form.

In In one embodiment, the FFAP is water soluble. In one embodiment, the FFAP is dispersible in water.

In one embodiment, the FFAP is wettable by organic solvent. The term "organic solvent wettable" refers to a material which, when formed into a film, is wettable by organic solvents In one embodiment, wettable materials produce films which are wettable by phenylhexane with a contact angle not greater than 40 ° used, the term "contact angle" is the angle Φ, shown in 1 mean. For a droplet of liquid medium, the angle Φ is defined by the intersection of the plane of the surface and a line from the outer edge of the droplet to the surface. Furthermore, the angle Φ is measured after the droplet, after being applied, has reached an equilibrium position on the surface, ie the "static contact angle." The film of the organic solvent wettable fluorinated polymeric acid is shown as a surface Embodiment, the contact angle is not greater than 35 ° In one embodiment, the contact angle is not greater than 30 ° The methods for measuring contact angles are known.

To Examples of suitable polymeric backbones include but not limited to polyolefins, polyacrylates, polymethacrylates, Polyimides, polyamides, polyaramides, polyacrylamides, polystyrenes and Copolymers thereof, all of which are fully fluorinated.

In one embodiment, the acidic groups are sulfonic acid groups or sulfonimide groups. A sulfonimide group has the formula: -SO ₂ -NH-SO ₂ -R where R is an alkyl group.

In one embodiment, the acidic groups are on a fluorinated side chain. In one version The fluorinated side chains are selected from alkyl groups, alkoxy groups, amido groups, ether groups and combinations thereof, all of which are fully fluorinated.

In In one embodiment, the FFAP has a perfluorinated olefin backbone with pendant perfluorinated alkylsulfonate, perfluorinated Ethersulfonat-, perfluorinated ester sulfonate or perfluorinated Ethersulfonimidgruppen. In one embodiment, this is Polymer is a copolymer of 1,1-difluoroethylene and 2- (1,1-difluoro-2- (trifluoromethyl) allyloxy) -1,1,2,2-tetrafluoroethanesulfonic acid. In one embodiment, the polymer is a copolymer of ethylene and 2- (2- (1,2,2-trifluorovinyloxy) -1,1,2,3,3,3-hexafluoropropoxy) -1,1,2,2-tetrafluoroethanesulfonic acid. These copolymers can be used as the corresponding sulfonyl fluoride polymer can be prepared and then in the sulfonic acid form being transformed.

In In one embodiment, the FFAP is homopolymer or copolymer of a fluorinated and partially sulfonated poly (arylene ether sulfone). The copolymer may be a block copolymer.

wo:
R_f aus perfluoriertem Alkylen, perfluoriertem Heteroalkylen, perfluoriertem Arylen und perfluoriertem Heteroarylen ausgewählt ist, welches mit einem oder mehreren Ethersauerstoffatomen substituiert sein kann; und
n mindestens 4. istIn one embodiment, the FFAP is a sulfonimide polymer having Formula IX:

Where:
R _{f is selected} from perfluorinated alkylene, perfluorinated heteroalkylene, perfluorinated arylene and perfluorinated heteroarylene which may be substituted with one or more ether oxygen atoms; and
n is at least 4.

In one embodiment of Formula IX, R _{f is} a perfluoroalkyl group. In one embodiment, R _{f is} a perfluorobutyl group. In one embodiment, R _f contains ether oxygen atoms. In one embodiment, n is greater than 10.

wo:
R¹⁵ eine perfluorierte Alkylengruppe oder eine perfluorierte Heteroalkylengruppe ist;
R¹⁶ eine perfluorierte Alkyl- oder eine perfluorierte Arylgruppe ist; und
a 0 oder eine ganze Zahl von 1 bis 4 ist.In one embodiment, the FFAP comprises a perfluorinated polymer backbone and a side chain of Formula X:

Where:
R ^{15 is} a perfluorinated alkylene group or a perfluorinated heteroalkylene group;
R ^{16 is} a perfluorinated alkyl or perfluorinated aryl group; and
a is 0 or an integer from 1 to 4.

wo:
R¹⁶ eine perfluorierte Alkyl- oder eine perfluorierte Arylgruppe ist;
c unabhängig 0 oder eine ganze Zahl von 1 bis 3 ist; und
n mindestens 4 ist.In one embodiment, the FFAP has the formula XI:

Where:
R ^{16 is} a perfluorinated alkyl or perfluorinated aryl group;
c is independently 0 or an integer from 1 to 3; and
n is at least 4.

The synthesis of FFAPs is in, for example, A. Feiring et al., J. Fluorine Chemistry 2000, 105, 129-135 ; A. Feiring et al., Macromolecules 2000, 33, 9262-9271 ; DD Desmarteau, J. Fluorine Chem. 1995, 72, 203-208 ; AJ Appleby et al., J. Electrochem. Soc. 1993, 140 (1), 109-111 ; and Desmarteau, U.S. Patent 5,463,005 been described.

In one embodiment, the FFAP also comprises a repeating unit derived from at least one perfluorinated ethylenically unsaturated compound. The perfluoroolefin comprises 2 to 20 carbon atoms. Representative perfluoroolefins include, but are not limited to, tetrafluoroethylene, hexafluoropropylene, perfluoro (2,2-dimethyl-1,3-dioxole), perfluoro (2-methylene-4-methyl-1,3-dioxolane), CF ₂ = CFO (CF ₂ ) _t CF = CF ₂ , where t is 1 or 2, and R _f "OCF = CF ₂ , wherein R _f " is a saturated perfluoroalkyl group of 1 to about 10 carbon atoms. In one embodiment, the comonomer is tetrafluoroethylene.

In In one embodiment, the FFAP is a colloid-producing polymeric acid. As used herein, the term "colloid-producing" Materials which are insoluble in water and colloids when dispersed in an aqueous medium become. The colloid-producing polymeric acids typically have a molecular weight in the range of about 10,000 to about 4,000,000. In one embodiment, the polymeric acids a molecular weight of about 100,000 to about 2,000,000. The colloid particle size typically ranges from 2 nanometers (nm) to about 140 nm. In In one embodiment, the colloids have a particle size from 2 nm to about 30 nm. Any fully fluorinated colloid-producing polymer Material with acidic protons can be used.

Some the polymers described above may be in non-acid form, z. B. as salts, esters or sulfonyl fluorides produced. she are described for the preparation of conductive compositions below, converted to the acid form.

4. Cations

The cation concentration is in the range of 5 x 10 ^-5 to 0.2 moles of cation per gram of doped conductive polymer. In one embodiment, the concentration is 5 x 10 ^-4 to 0.2 moles of cation per gram of doped conductive polymer; in one embodiment, 1 x 10 ^-3 to 0.2 moles of cation per gram of doped conductive polymer; in one embodiment, 1 x 10 ^-3 to 0.1 moles of cation per gram of doped conductive polymer.

In In one embodiment, the cations are the acidic ones Replace protons, organic cations. Examples of organic Cations include, but are not limited to, ammonium ions with one or more alkyl groups. In one embodiment have the alkyl groups of 1-3 carbon atoms.

In one embodiment, the cations that replace the acidic protons are inorganic cations. Examples of inorganic cations include, but are not limited to, ammonium and cations from Groups 1 and 2 of the Periodic Table. In one embodiment, the inorganic cations are selected from the group consisting of NH ₄ ⁺ , Na ⁺ , K ⁺ and combinations thereof.

5. Preparation of the doped electrically conductive polymer composition

In In one embodiment, the doped electrically conductive Polymer composition by the oxidative polymerization of the precursor monomers generated in the presence of the FFAP. In one embodiment the precursor monomers two or more conductive Precursor monomers. In one embodiment the monomers are an intermediate precursor monomer with the structure A-B-C where A and C are precursor monomers represent which may be the same or different, and B represents a non-conductive precursor monomer. In one embodiment, the intermediate Precursor monomer with one or more conductive Polymerized precursor monomers.

In one embodiment, the oxidative polymerization is carried out in a homogeneous aqueous solution. In another embodiment, the oxidative polymerization is carried out in an emulsion of water and an organic solvent. In general, some water is present to obtain adequate solubility of the oxidant and / or catalyst. Oxidizing agents such as ammonium persulfate, sodium persulfate, potassium persulfate and the like can be used. A cataly may also be present, such as iron (III) chloride or ferric sulfate. The resulting polymerized product will be a solution, dispersion or emulsion of the conductive polymer in conjunction with the FFAP. In one embodiment, the intrinsically conductive polymer is positively charged and the charges are balanced by the FFAP anion.

In In one embodiment, the method for Make an aqueous dispersion of the new conductive Polymer composition by generating a reaction mixture Combine water, precursor monomer, at least one FFAP and an oxidizing agent, in any order, a, with the proviso that at least one share the FFAP is present if at least one of the precursor monomer and the oxidizing agent is added.

• (a) Bereitstellen einer wässerigen Lösung oder Dispersion von einem FFAP;
• (b) Hinzufügen eines Oxidationsmittels zu der Lösung oder Dispersion von Schritt (a); und
• (c) Hinzufügen von Vorläufermonomer zu dem Gemisch von Schritt (b).

In an embodiment, the method of making the doped conductive polymer composition comprises:

• (a) providing an aqueous solution or dispersion of a FFAP;
• (b) adding an oxidizing agent to the solution or dispersion of step (a); and
• (c) adding precursor monomer to the mixture of step (b).

In In another embodiment, the precursor monomer before adding the oxidizing agent to the aqueous Solution or dispersion of the FFAP added. Prominent Step (b), which is adding oxidant, is then executed.

In In another embodiment, a mixture of water and the precursor monomer, in one concentration typically in the range of about 0.5% to about 4.0% by weight entire forerunner monomer. This precursor monomer mix becomes the aqueous solution or dispersion of FFAP, and step (b) above, which adds of oxidizing agent is carried out.

In In another embodiment, the aqueous Polymerization mixture a polymerization catalyst, such as Ferric sulfate, ferric chloride and the like. The catalyst is added before the last step. In a In another embodiment, a catalyst is used together with an oxidizing agent added.

In In one embodiment, the polymerization is in the presence of codispersing fluids, which are miscible with water. Examples of suitable codispersing Liquids include, but are not limited to to be ethers, alcohols, alcohol ethers, cyclic ethers, ketones, Nitriles, sulfoxides, amides and combinations thereof. In one embodiment the codispersing liquid is an alcohol. In a Embodiment is the codispersing liquid an organic solvent selected from n-propanol, isopropanol, t-butanol, dimethylacetamide, dimethylformamide, N-methylpyrrolidone and mixtures thereof. In general, the Amount of codispersant liquid less than about Be 60 vol .-%. In one embodiment, the amount is of codispersing liquid less than about 30% by volume. In one embodiment, the amount of codispersing Liquid between 5 and 50 vol .-%. The use of a codispergierenden liquid reduced in the polymerization the particle size significantly and improves the Filterability of the dispersions. In addition, buffer materials, obtained by this method, an increased viscosity and films made from these dispersions are of high quality.

The Codispergierende liquid can at any point in the process are added to the reaction mixture.

In In one embodiment, the polymerization is in the presence a co-acid, which is a Brønsted acid is. The acid can be an inorganic acid, such as for example, HCl, sulfuric acid and the like, or an organic acid such as acetic acid or p-toluenesulfonic acid. Alternatively, the acid a water-soluble polymeric acid, such as Poly (styrenesulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid or the like, or a second FFAP as described above. Combinations of acids can be used.

The co-acid may be added to the reaction mixture at any point in the process prior to the addition of either the oxidant or the precursor monomer, whichever is added last. In one embodiment, the co-acid is added before both the precursor monomers and the FFAP, and the oxidant is added last. In an off For example, the co-acid is added prior to the addition of the precursor monomers, followed by the addition of the FFAP, and the oxidant is added last.

In In one embodiment, the polymerization is in the presence of both a codispersing liquid and carried out a co-acid.

In In one embodiment, a reaction vessel is first with a mixture of water, codispersing agent in the form of Loaded alcohol and inorganic cocoa acid. To become this, in turn, the precursor monomers, an aqueous Solution or dispersion of FFAP and an oxidizing agent added. The oxidizer becomes slow and drops added to the formation of localized areas with high To prevent ion concentration, which destabilize the mixture can. The mixture is stirred and the reaction is then allowed to drain at a controlled temperature. When the polymerization is complete, the reaction mixture becomes treated with a strong acid-cation resin, stirred and filtered and then treated with a base anion exchange resin, stirred and filtered. Alternative orders of addition can be used as discussed above.

In the method of making the novel conductive polymer composition is the molar ratio of oxidant to total Precursor monomer generally in the range of 0.1 to 2.0 and in one embodiment is 0.4 to 1.5. The molar ratio from FFAP to total precursor monomer is generally in in the range of 0.3 to 10. In one embodiment the ratio in the range of 1 to 7. The total solids content is generally in the weight percent range of about 0.5% to 15% and in one embodiment from about 2% to 7%. The reaction temperature is generally in the range of about 4 ° C to 50 ° C; in one embodiment about 20 ° C to 35 ° C; in one embodiment about 10 ° C to 25 ° C. The molar ratio from optional co-acid to precursor monomer about 0.05 to 4. The reaction time is generally within the range from about 1 to about 30 hours.

6. Replacement of acidic protons with cations

In One embodiment is a conductive polymer composition under conditions suitable for acidic protons with cations in contact with at least one ion exchange resin brought. The composition may be of one or more types treated by ion exchange resins simultaneously or sequentially become.

ion exchange is a reversible chemical reaction where an ion is in a fluid Medium (such as an aqueous dispersion) for a similarly charged ion linked to one immobile solid particles that are insoluble in the fluid medium is, is exchanged. The term "ion exchange resin" is used herein to refer to all such substances. The resin is due to the crosslinked nature of the polymeric carrier, to which the ion-exchanging groups are linked, insolubilized. Ion exchange resins are used as cation exchangers or anion exchanger classified. Have cation exchanger positively charged mobile ions, available for replacement, typically metal ions such as sodium ions. anion exchanger have exchangeable ions which are negatively charged, typically hydroxide ions.

In One embodiment is a first ion exchange resin a cation-acid exchange resin used in metal ion, typically sodium ion form. A second ion exchange resin is a basic anion exchange resin. Both acidic cation-proton exchange resins as well as basic anion exchange resins can be used become. In one embodiment, the acidic cation exchange resin is an inorganic acid-cation exchange resin such as a sulfonic acid cation exchange resin. To sulfonic acid cation exchange resins, considered for use in the practice of Invention include, for example, sulfonated styrene-divinylbenzene copolymers, sulfonated crosslinked styrene polymers, phenol-formaldehyde-sulfonic acid resins, Benzene-formaldehyde-sulfonic acid resins and mixtures thereof. In another embodiment, the acidic cation exchange resin is an organic acid-cation exchange resin such as Carboxylic acid, acrylic or phosphorus cation exchange resin. Furthermore may be mixtures of different cation exchange resins be used.

In another embodiment, the basic, anionic exchange resin is a tertiary amine anion exchange resin. Tertiary amine anion exchange resins contemplated for use in the practice of the invention include, for example, tertiary aminated styrene-divinylbenzene copolymers, tertiary aminated crosslinked styrene polymers, tertiary aminated phenol-formaldehyde resins, tertiary-aminated benzene Formaldehyde resins and mixtures thereof. In a further embodiment this is basic, anionic exchange resin, a quaternary amine anion exchange resin, or mixtures of these and other exchange resins.

In In one embodiment, both types of resins become simultaneously to a liquid composition comprising the electrically conductive polymer and FFAP, added and for at least about 1 hour, z. From about 2 hours to about 20 hours with the liquid composition left. The Ion exchange resins can then be removed by filtration from the Dispersion are removed. The size of the filter is chosen so that the relatively large Ion exchange resin particles are removed, while the smaller Go through the dispersion particles. In general, about one to five grams of ion exchange resin per gram of new conductive polymer composition used.

In In some embodiments, the acidic protons pass through the addition of an aqueous basic solution replaced. Basic compounds include hydroxides, carbonates and bicarbonates. Examples of such a solution include, but are not limited to, sodium hydroxide, Ammonium hydroxide, tetramethylammonium hydroxide and the like.

In In one embodiment, more than 50% of the acid protons become replaced with cations. In one embodiment, more will be done replaced as 60%; in one embodiment, more than 75% replaced; in one embodiment, more than 90% replaced.

7. Electronic devices

In Another embodiment of the invention will be electronic Devices comprising at least one layer made from the conductive polymer composition described herein, provided. The term "electronic device" is intended to mean a device containing one or more organic semiconductor layers or materials. An electronic device includes, but is not limited to: (1) one Device that converts electrical energy into radiation (eg. A light emitting diode, a light emitting diode display, a diode laser or a lighting panel), (2) a device, which detects a signal using an electronic process (eg, a photodetector, a photoconductivity cell, a photoresistor, a photoelectric relay, a phototransistor, a Photocell, an infrared ("IR") detector or a biosensor), (3) a device that converts radiation into electrical energy (eg, a photovoltaic device or solar cell), (4) a Device including one or more electronic components, which include one or more organic semiconductor layers (eg, a transistor or a diode) or any combination of devices in the items (1) to (4).

In an embodiment includes the electronic Device at least one electroactive layer, positioned between two electrical contact layers, the device further includes the bilayer. The term "electroactive" should, when referring to a layer or a material, a Layer or a material that has electronic or electrical radiation properties shows. A material of an electroactive layer can be radiation emit or change in the concentration of Electron-hole pairs show when receiving radiation.

As in 2 1, a typical device 100, an anode layer 110, a buffer layer 120, an optional hole transport layer 130, an electroactive layer 140, an optional electron injection / transport layer 140, and a cathode layer 160 have been shown.

The Device can not be a carrier or a substrate (not shown) adjacent to the anode layer 110 or the cathode layer 160 may be. Most frequently the carrier is adjacent to the anode layer 110 Carriers can be flexible or rigid, organic or inorganic be. Examples of carrier materials include but without being limited to glass, ceramics, metal, and plastic films.

The anode layer 110 is an electrode that is more effective for injecting holes as compared to the cathode layer 160. The anode may include materials including a metal, mixed metal, an alloy, a metal oxide, or mixed oxide. Suitable materials include the mixed oxides of Group 2 elements (ie, Be, Mg, Ca, Sr, Ba, Ra), Group 11 elements, Group 4, 5 and 6 elements, and Group 8 transition elements -10. If the anode layer 110 is to be transparent, mixed oxides of the elements of groups 12, 13 and 14, such as indium tin oxide, may be used. As used herein, the term "mixed oxide" refers to oxides with two or more different cations selected from Group 2 elements or Group 12, 13, or 14 elements. Some nonlimiting, specific examples of materials for anode layer 110 include, but are not limited to, indium Tin oxide ("ITO"), indium zinc oxide, aluminum tin oxide, gold, silver, copper and nickel The anode may also comprise an organic material, especially a conductive polymer such as polyaniline, including example materials, as described in "Flexible light-emitting diodes made of soluble conducting polymer"("Flexible Light-Emitting Diodes Made of Soluble Conductive Polymer") Nature 357: 477-479 (June 11, 1992) , At least one of the anode and cathode should be at least partially transparent to allow the generated light to be observed.

The Anode layer 110 may be formed by a chemical or physical Vapor deposition method or spin coating method be generated. Chemical vapor deposition can be called plasma-enhanced chemical vapor deposition ("PECVD") or organometallic chemical vapor deposition ("MOCVD") become. Physical vapor deposition can take all forms of sputtering, including ion beam sputtering, as well as electron beam evaporation and resistance evaporation. To special Forms of physical vapor deposition include rf magnetron sputtering and Inductively Coupled Plasma-Physical Vapor Deposition ("IMP-PVD"). These deposition techniques are within the specialist fields of semiconductors Manufacturing known.

In In one embodiment, the anode layer 110 is during a lithographic step structured. The structure can vary as desired. The layers can before applying the material of the first electrical contact layer by, for example, positioning a structured mask or a Resists on the first flexible composite barrier structure in FIG a structure are created. Alternatively, the layers can Applied as a total layer (also overlapping application called) and then using, for example, a structured resist layer and wet chemical or dry etching techniques are structured. Other procedures for structuring, which are known in the art also be used.

The conductive polymer compositions described herein are suitable as the buffer layer 120. The term "buffer layer" or "buffer material" is intended to be electrically conductive or semiconducting materials mean and can be one or multiple functions in an organic electronic device have, but are not limited to, planarization of the underlying layer, charge transport and / or charge injection properties, Trapping contaminants, such as oxygen or Metal ions, and other aspects, include the performance facilitate or to the organic electronic device improve. The buffer layer is usually used a variety of techniques known in the art on substrates applied. Typical deposition techniques include Vapor deposition, liquid separation (continuous and discontinuous techniques) and heat transfer. To continuous deposition techniques include, without but to be limited to, spin coating, gravure coating, Curtain coating, dip coating, slot die coating, Spray coating and continuous die coating. Discontinuous deposition techniques include, without but to be limited to inkjet, gravure, and Screen printing.

An optional layer 130 may be present between the buffer layer 120 and the electroactive layer 140. This layer may comprise hole transport materials. Examples of hole transport materials are, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, (Encyclopedia of Chemical Technology, Fourth Edition), Vol. 18, pp. 837-860, 1996, by Y. Wang been summarized. Both hole-transporting molecules and polymers can be used. Commonly used hole-transporting molecules include, but are not limited to: 4,4 ', 4 "-tris (N, N-diphenylamino) -triphenylamine (TDATA); 4,4 ', 4 "-tris (N-3-methylphenyl-N-phenylamino) -triphenylamine (MTDATA); N, N'-diphenyl-N, N'-bis (3-methylphenyl) - [1,1'-biphenyl] -4,4'-diamine (TPD); 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC); N, N'-bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl) - [1,1 '- (3,3'-dimethyl) biphenyl] -4,4'-diamine (ETPD) ; Tetrakis (3-methylphenyl) -N, N, N ', N'-2,5-phenylenediamine (PDA); α-phenyl-4-N, N-diphenylaminostyrene (TPS); p- (diethylamino) benzaldehyde-diphenylhydrazone (DEH); Triphenylamine (TPA); Bis [4- (N, N -diethylamino) -2-methylphenyl] (4-methylphenyl) methane (MPMP); 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline (PPR or DEASP); 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB); N, N, N ', N'-tetrakis (4-methylphenyl) - (1,1'-biphenyl) -4,4'-diamine (TTB); N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) benzidine (α-NPB); and porphyrinic compounds such as copper phthalocyanine. Commonly used hole transporting polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl) polysilane, poly (dioxythiophenes), polyaniline, and polypyrroles. It is also possible to use hole-transporting polymers by doping hole-transporting polymers To obtain molecules such as those mentioned above in polymers such as polystyrene and polycarbonate.

In In some embodiments, the hole transport layer comprises a hole transport polymer. In some embodiments the hole transport polymer is a distyrylaryl compound. In some Embodiments, the aryl group has two or more condensed aromatic rings. In some embodiments the aryl group is an acene. The term "acen" denotes as used herein, a parent hydrocarbon component which two or more ortho-fused benzene rings in a straight contains linear arrangement.

In In some embodiments, the hole transport polymer is an arylamine polymer. In some embodiments it is a copolymer of fluorene and arylamine monomers.

In In some embodiments, the polymer has crosslinkable groups. In some embodiments, crosslinking may be accomplished by a Heat treatment and / or exposure to UV or visible Radiation be accomplished. Examples of networkable Groups include, but are not limited to, vinyl, Acrylate, perfluorovinyl ether, 1-benzo-3,4-cyclobutane, siloxane and Methylester. Crosslinkable polymers can be used in production benefit from OLEDs through a solution process. The Application of a soluble polymeric material to a Layer to produce, which subsequent to the deposition can be converted into an insoluble film the fabrication of solution-processed multilayer OLED devices allow for free slice resolution problems.

Examples of crosslinkable polymers can be found in, for example, published US patent application 2005-0184287 and published PCT application WO 2005/052027 being found.

In In some embodiments, the hole transport layer comprises a polymer which is a copolymer of 9,9-dialkylfluorene and triphenylamine is. In some embodiments, the polymer is a copolymer of 9,9-dialkylfluorene and 4,4'-bis (diphenylamino) biphenyl. In some In embodiments, the polymer is a copolymer of 9,9-dialkylfluorene and TPB. In some embodiments, the polymer is a Copolymer of 9,9-dialkylfluorene and NPB. In some embodiments is the copolymer of a third comonomer selected from (vinylphenyl) diphenylamine and 9,9-distyrylfluorene or 9,9-di (vinylbenzyl) fluorene, produced.

Depending on the application of the device, the electroactive layer 140 may be a light emitting layer activated by an applied voltage (such as in a light emitting diode or light emitting electrochemical cell), a layer of material responsive to radiant energy and with or without one applied bias voltage generates a signal (such as in a photodetector). In one embodiment, the electroactive material is an organic electroluminescent ("EL") material Any EL material may be used in the devices, including, but not limited to, organic fluorescent compounds with small molecules, fluorescent and phosphorescent metal complexes, Examples of fluorescent compounds include, but are not limited to, pyrene, perylene, rubrene, coumarin, derivatives thereof, and mixtures thereof Examples of metal complexes include, but are not limited to, metal chelated oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq3); cyclometalated electroluminescent iridium and platinum compounds such as complexes of iridium with phenylpyridine, phenylquinoline or phenylpyrimidine ligands as disclosed in Petrov et al., U.S. Patent 6,670,645 and the published PCT applications WO 03/063555 and WO 2004/016710 and organometallic complexes described in, for example, the published PCT applications WO 03/008424 . WO 03/091688 and WO 03/040257 , and mixtures thereof. Electroluminescent emitting layers comprising a charge-carrying host material and a metal complex have been described by Thompson et al. in the U.S. Patent 6,303,338 and Burrows and Thompson in published PCT applications WO 00/70655 and WO 01/41512 been described. Examples of conjugated polymers include, but are not limited to, poly (phenylenevinylenes), polyfluorenes, poly (spirobifluorenes), polythiophenes, poly (p-phenylenes), copolymers thereof, and mixtures thereof.

The optional layer 150 may function both to facilitate electron injection / transport and to serve as a constraint layer to prevent quenching reactions at layer interfaces. More specifically, layer 140 may promote electron mobility and reduce the likelihood of a deterrent reaction if layers 140 and 160 otherwise would be in direct contact. Examples of materials for optional layer 150 include, but are not limited to, metal chelated oxinoid compounds such as bis (2-methyl-8-quinolinolato) (para-phenyl-phenolato) aluminum (III) (BAlQ). and tris (8-hydroxyquinolato) aluminum (Alq3); Tetrakis (8-hydroxychinoli nato) zirconium; Azole compounds such as 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD), 3- (4-biphenylyl) -4-phenyl-5- (4-t -butylphenyl) -1,2,4-triazole (TAZ) and 1,3,5-tri (phenyl-2-benzimidazole) benzene (TPBI); Quinoxaline derivatives such as 2,3-bis (4-fluorophenyl) quinoxaline; Phenanthroline derivatives such as 9,10-diphenylphenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); and any one or more combinations thereof. Alternatively, the optional layer 150 may be inorganic and include BaO, LiF, Li ₂ O, or the like.

The Cathode layer 160 is an electrode for injecting electrons or negative charge carriers is particularly effective. The Cathode layer 160 may be any metal or nonmetal with a lower work function than that of the first electrical Contact layer (in this case, the anode layer 110). As used here, the term "lower work function" a material with a work function is not larger as about 4.4 eV. As used here, "higher Work function "a material with a work function of at least about 4.4 eV mean.

materials for the cathode layer can be made of alkali metals Group 1 (eg Li, Na, K, Rb, Cs,), the metals of the group 2 (e.g., Mg, Ca, Ba, or the like), the metals of the group 12, the lanthanides (eg Ce, Sm, Eu or the like) and the Actinides (eg, Th, U, or the like) can be selected. Materials such as aluminum, indium, yttrium and combinations of which can also be used. To special non-limiting examples of materials for the cathode layer 160 include, but are not limited to, barium, Lithium, cerium, cesium, europium, rubidium, yttrium, magnesium, samarium and alloys and combinations thereof.

The Cathode layer 160 is usually characterized by a chemical or physical vapor deposition process. In some Embodiments, the cathode layer is structured as discussed above with respect to the anode layer 110 is.

Other Layers in the device can be made of any materials which are known to be produced Consider the function of such layers to be served, are usable in such layers.

In In some embodiments, an encapsulation layer is used (not shown) applied over the contact layer 160, to the entry of undesirable components, such as water and oxygen, into the device 100 to prevent. Such components can be harmful Have an impact on the organic layer 140. In one embodiment For example, the encapsulating layer is a barrier layer or a film. In In one embodiment, the encapsulation layer is a Glass lid.

Even though it is not obvious that the Device 100 may comprise additional layers. Other Layers known in the art or otherwise known can be used. In addition, any of the above-described layers, two or more sub-layers comprise or may form a laminar structure. Alternatively you can some or all of the layers are treated, specially surface treated, be the charge carrier transport efficiency or other physical To increase the characteristics of the devices. The choice of materials for each of the component layers is preferably determined by the goals, a device with to provide high efficiency of the device, with considerations on the service life of the device, factors of manufacturing time and complexity and other considerations recognized by those skilled in the art be matched. It is recognized that determining the optimum Components, component configurations and compositional identities would be routine for the nominal professional.

In In one embodiment, the various layers the following range of thicknesses: anode 110, 500-5000 Å, in one embodiment 1000-2000 Å; Buffer layer 120, 50-2000 Å, in one embodiment 200-1000 Å; optional hole transport layer 130, 50-2000 Å, in one embodiment 200-1000 Å; photoactive layer 140, 10-2000 Å, in one embodiment 100-1000 Å; optional electron transport layer 150, 50-2000 Å, in one embodiment 100-1000 Å; Cathode 160, 200-10000 Å, in one embodiment 300-5000 Å. The location of the electron-hole recombination zone in the device, and so the emission spectrum of the device, can by the relative thickness of each layer is affected. So the thickness of the electron transport layer should be chosen so be that the electron-hole recombination in the light emitting layer is. The desired ratio of layer thicknesses is determined by the exact nature of the materials used depend.

In operation, a voltage is supplied from a suitable power supply (not shown) to the front panel Direction 100 created. The current therefore passes through the layers of device 100.

electrons enter the organic polymer layer, where they are photons release. In some OLEDs, called OLED displays with active Matrix, can be individual applications of photoactive organic films independently by the passage of electricity be excited, which leads to individual pixels of light emission. In some OLEDs, called passive matrix OLED displays, you can Plots of photoactive organic films through rows and Columns are excited by electrical contact layers.

EXAMPLES

The The concepts described here will be further described in the following examples described which are those described in the claims Not limit the scope of the invention.

COMPARATIVE EXAMPLE A

This comparative example illustrates the effect of pH on the performance of the device when Baytron P AI4083 ^® is used as the buffer layer.

Baytron-P AI4083 (HC Starck, GmbH, Leverkusen, Germany) is a poly (3,4-dioxyethylene thiophene) / poly (styrenesulfonic acid), PEDOT / PSSA. It was measured that the sample of Baytron-P AI4083 as obtained had 1.5% (w / w) solid of PEDOT / PSSA and pH 1.7 (Comparative Example A-1). About 100 g of the Baytron-P was added with aqueous ~ 1.0 M NH ₄ OH solution until the pH reached 2.6 (Comparative Example A-2). Another 100 g of the Baytron-P was adjusted to pH 3.9 (Comparative Example A-3).

Comparative Examples A-1, A-2 and A-3 were spin-coated on glass / ITO backlight substrates (30 mm x 30 mm). Each ITO substrate with an ITO thickness of 100 to 150 nm consists of 3 pieces of 5 mm × 5 mm pixels and 1 piece of 2 mm × 2 mm pixels for light emission. Once spin-coated on ITO substrates, the films were baked first at 130 ° C in air for 10 minutes and then at 200 ° C for 10 minutes. The thickness of the Baytron P layer after baking was 40 nm. The Baytron P layer was coated with an about 60 nm thick film of Dow Chemicals electroluminescent polymer Lumination Green 1303 (from 1% wt / vol. Solution in p-xylene) in air spin-coated. After baking the electroluminescent film at 130 ° C in a drying oven for 30 minutes, a cathode consisting of 3 nm of Ba and 260 nm of Al was thermally evaporated at a pressure of less than 4 × 10 ^-6 Torr. Encapsulation of the devices was accomplished by adhering a glass slide to the back of the devices using a UV-curable epoxy resin.

Table 1 shows the effectiveness of a light emitting device at 200, 500, 1000 and 2000 nits (Cd / m ²⁾ for devices fabricated with Baytron-P ^® -AI4083 buffer layers with three different pH. The data show for Baytron-P with all three pH's that the efficiency increases slowly as the luminance increases from 200 nits to 2000 nits. As the pH increases, the efficacy decreases, showing a deleterious effect of the pH on the performance of the device.

EXAMPLE 1

This example illustrates the cation composition and the operating behavior of the device from a poly (3,4-dioxyethylenthiophen) with low pH, PEDOT / Nafion ^®, a poly (tetrafluoroethylene) / perfluorethersulfonsäure), for comparison with Baytron-P in Comparative Example A.

A dispersion of polydioxythiophene and colloid-forming polymeric acid, prepared using PEDOT and Nafion ^® a commercial product that can be bought by the EI DuPont de Nemours and Company, Wilmington DE, was ^® using an aqueous colloidal Nafion dispersion with a EW (Acid Equivalent Weight) made of 1000. The Nafion ^® dispersion with 25% (wt./wt.) Was prepared using a procedure similar to the procedure in U.S. Patent 6,150,426 Example 1, part 2, except that the temperature was about 270 ° C, and was then diluted with water to produce a 12.0% (w / w) dispersion for the polymerization.

1,2-ethylenedioxythiophene - ( "EDOT") - monomers were reacted with the Nafion ^® dispersion, as described in published U.S. patent application 2004 to 02,542,970.

After the reaction was complete, about 18.5 hours, 200 grams each of Dowex M31 and Dowex M43 ion exchange resins and 225 grams deionized water were added to the reaction mixture and stirred for 4 hours at 120 rpm. The ion exchange resins were finally filtered from the suspension through VWR 417 filter paper. The entire filtered dispersion was then pumped once through a port at 5000 psi. The pH of the dispersion was 1.9 and 130 ° C baked films applied by spin coating from the dispersion had a conductivity of 9.4 x 10 ^-3 S / cm at room temperature.

It was determined that the dispersion of 5.34% total solids consisting essentially of PEDOT and Nafion ^® contained. Ion chromatography analysis shows that the dispersion contains only 62.7 × 10 ^-6 g NH ₄ ⁺ per one ml dispersion. The ion concentration is approximately equivalent to ^{3.5x10 -6} moles NH ₄ ⁺ per one gram of the dispersion. Thus, the cation concentration was 0.7 × 10 ^-4 mol NH ₄ ⁺ per gram of solids (total of PEDOT and Nafion ^®). The ammonium cations are the residual amount of the ammonium persulfate oxidizer. Based on the solids% and the amount of Nafion ^® used in the polymerization, the dispersion contains about 51 × 10 ^-6 mol of sulfonic acid group per one gram of the dispersion. This reveals that about 15% of the sulfonic acid group in the solid forms ammonium salt. Some of the remaining sulfonic acid anions form complexes with partially oxidized poly (3,4-ethylenedioxythiophene), PEDOT, to balance the positive charges on PEDOT backbones. It is reasonably believed that an approximately 3.5 EDOT unit is a deficient electron. The total number of EDOT used in the polymerization is 14.6 x 10 ^-6 per gram of the dispersion. It is therefore estimated that 4.2 x 10 ^-6 moles of sulfonic acid group are used as anions to balance the partially oxidized PEDOT. As a result, about 80% of the sulfonic acid still remains as an acid in the solid. It should be understood that ammonium cations could be completely removed with additional treatment with a proton exchange resin.

The pH-1,9-PEDOT / Nafion ^® was made to light emitting devices by the procedure indicated in Comparative Example A was followed. The thickness of PEDOT / Nafion ^® films, baked first at 130 ° C in air for 10 minutes and then at 200 ° C for 10 minutes, was 70 nm. The thickness of lumination Green 1303 baked at 130 ° C in a drying cabinet for 30 minutes, was 60 nm. A cathode consisting of 3 nm of Ba and 260 nm of Al was thermally evaporated at a pressure of less than 4 × 10 ^-6 Torr. Encapsulation of the devices has been achieved; by gluing a glass slide to the back of the devices using a UV-curable epoxy resin.

The data of the device of this example, summarized in Table 1, show that PEDOT / Nafion ^® increases at pH 1.9 at low luminance immediately to high efficiency. It also provides much higher efficacy than Baytron-P at all pH levels using Luminance Green 1303. The T-50 lifetime (luminance drops to one half of the original brightness of 5050 nits) is given in Table 1. Table 1 also shows that PEDOT / Nafion ^® receives high efficacy upright regardless of pH and cation concentration.

EXAMPLE 2

This example illustrates cation composition and device performance of the poly (3,4-dioxyethylenthiophen) / Nafion ^® manufactured in Example 1 but adjusted with an aqueous NaOH solution to pH 6.4.

The PEDOT / Nafion ^® dispersion prepared in Example 1, containing 5.34% solids and has a pH of 1.9. About 200 ml of the dispersion was added with 1N sodium hydroxide-water solution until the pH reached 6.4. The dispersion was measured to contain 5.33% solids. 130 ° C. baked films applied by spin coating from the 6.4 pH dispersion have a conductivity of 2.9 × 10 ^-4 S / cm at room temperature. Ion chromatography analysis shows that the dispersion contains 963 x 10 ^-6 g Na ⁺ and 70.6 x 10 ^-6 g NH ₄ ⁺ per one ml dispersion. The ion concentration is approximately equivalent to 42 × 10 ^-6 mol of Na ⁺ and 3.9 x 10 ^-6 moles of NH ₄ ⁺ per one gram of the dispersion, so that the combined cation concentration 46 x 10 ^-6 mol (NH ₄ ⁺ and Na ⁺ ) per gram of the dispersion. Thus, the total cation concentration was 8.6 × 10 ^-4 mol cations (mainly Na ⁺⁾ per gram of solids (total of PEDOT and Nafion ^®). Based on the solid%, and the amount of Nafion ^® used in the polymerization, the dispersion contains about 51 × 10 ^-6 mol of sulfonic acid group per one gram of the dispersion. This reveals that about 90% of the sulfonic acid group in the solid forms sodium and ammonium salt. Some of the remaining sulfonic anions form complexes with partially oxidized 3,4-ethylenedioxythiophene (EDOT) to balance the positive charges. It is reasonably estimated that an approximately 3.5 EDOT unit is a deficient electron. The total number of EDOTs used in the polymerization is 14.6 x 10 ^-6 moles per gram Dispersion. It is therefore estimated that 4.2 x 10 ^-6 moles of sulfonic acid are used as anions to make up for the partially oxidized poly (EDOT). This results in only 2% of the sulfonic acid remaining as an acid in the solid.

The pH-6.4-PEDOT / Nafion ^®, containing mainly sodium cations was made in 1303 to light emitting devices using lumination Green was by the procedure given in Comparative Example A and Example 1 are followed. Data of the device of this example, summarized in Table 1, show that the PEDOT / Nafion ^®, adjusted with sodium cations of the low pH to pH 6.4, also at a low luminance immediately rises to a high efficiency. It also provides much higher efficacy than Baytron-P at all pH levels using Luminance Green 1303. The T-50 lifetime (luminance drops to one half of the original brightness of 4420 nits) is shown in Table 1. Table 1 also shows that PEDOT / Nafion ^® receives high efficacy upright regardless of pH and cation concentration.

EXAMPLE 3

This example illustrates cation composition and device performance of the poly (3,4-dioxy-ethylenthiophen) / Nafion ^® manufactured in Example 1 but adjusted with an aqueous NH ₄ OH solution to pH 6.4.

The PEDOT / Nafion ^® dispersion prepared in Example 1, contained 5.34% solids and has a pH of 1.9. About 200 ml of the dispersion was added with 1N ammonium hydroxide-water solution until the pH reached 6.4. The dispersion was measured to contain 5.49% solids. 130 ° C baked films obtained from the 6.4 pH dispersion have a conductivity of 6.8 x 10 ^-4 S / cm at room temperature. Ion chromatography analysis shows that the dispersion contains 745 x 10 ^-6 g of NH ₄ ⁺ per one ml of dispersion. The ion concentration is approximately equivalent to ^{41x10 -6} moles NH ₄ ⁺ per one gram of the dispersion. Thus, the cation concentration was 7.7 × 10 ^-4 mol NH ₄ ⁺ per gram of solids (total of PEDOT and Nafion ^®). Based on the solids% and the amount of Nafion ^®, used in the polymerization, the dispersion contains about 53 × 10 ^-6 mol of sulfonic acid group per one gram of the dispersion. This reveals that about 77% of the sulfonic acid groups in the solid form ammonium salt. Some of the remaining sulfonic anions form complexes with partially oxidized 3,4-ethylenedioxythiophene (EDOT) to balance the positive charges. It is reasonably estimated that an approximately 3.5 EDOT unit is a deficient electron. The total number of EDOTs used in the polymerization is 15.1 x 10 ^-6 moles per gram of the dispersion. It is therefore estimated that 4.3 x 10 ^-6 moles of sulfonic acid are used as anions to make up for the partially oxidized poly (EDOT). This results in about 15% of the sulfonic acid remaining as an acid in the solid.

The pH-6.4-PEDOT / Nafion ^®, containing ammonium cations was made in 1303 to light emitting devices using lumination Green was by the procedure given in Comparative Example 1 and Example 1 are followed. Data of the device of this example, summarized in Table 1, show that the PEDOT / Nafion ^®, set by the low pH with ammonium cations to high pH, also immediately at low luminance rises too high efficiency. It also provides much higher efficacy than Baytron-P at all pH levels using Luminance Green 1303. The T-50 lifetime (luminance drops to one half of the original brightness of 4630 nits) is shown in Table 1. Table 1 also shows that PEDOT / Nafion ^® receives high efficacy upright regardless of pH and cation concentration.

EXAMPLE 4

This example illustrates cation composition and operating behavior of the device from a polypyrrole / poly (tetrafluoroethylene / perfluorethersulfonsäure) with low pH ( "PPy / Nafion ^®").

A PPy used in this example / Nafion ^® dispersion was prepared using an aqueous colloidal Nafion ^® dispersion with an EW (acid equivalent weight) of the 1000th The Nafion ^® dispersion with 25% (wt./wt.) Was prepared using a procedure similar to the procedure in U.S. Patent 6,150,426 Example 1, part 2, prepared; except that the temperature was about 270 ° C, and was then diluted with water to produce a 12.0% (w / w) dispersion for the polymerization.

Pyrrole - ( "Py") - monomers were reacted with the Nafion ^® dispersion, as described in published US Patent Application 2005-0205860.

After the reaction was complete, about 29 hours, 100 g of each of Dowex M31 and Dowex M43 ion exchange resins and 100 g of deionized water were added to the reaction mixture and stirred for 2 hours at 120 rpm. The ion exchange resins were finally filtered from the suspension through VWR 417 filter paper. The pH of the dispersion was 2.35 and films baked at 130 ° C / 10 minutes had a conductivity of 5.4 × 10 ^-2 S / cm at room temperature.

It was determined that the dispersion contained 3.88% PPy / Nafion ^® -solids. Ion chromatography analysis shows that the dispersion contains only 93.4 x 10 ^-6 g of NH ₄ ⁺ per one ml of dispersion. The ion concentration is approximately equivalent to 5.2 x 10 ^-6 moles NH ₄ ⁺ per one gram of the dispersion. Thus, the cation concentration was 1.3 × 10 ^-4 mol NH ₄ ⁺ per gram of solids (total of PPy plus Nafion ^®). The ammonium cations are the residual amount of the ammonium persulfate oxidizer. Based on the solids% and the amount of Nafion ^®, used in the polymerization, the dispersion contains about 36.4 x 10 ^-6 moles of sulfonic acid group per one gram of the dispersion. This reveals that about 14% of the sulfonic acid group in the solid forms ammonium salt. Some of the remaining sulfonic anions form complexes with partially oxidized polypyrrole to balance the positive charges. It is estimated that an approximately 3.5 pyrrole unit is a deficient electron. The total number of pyrrole used in the polymerization is 36.4 x 10 ^-6 moles per gram of the dispersion. It is therefore estimated that 10 x 10 ^-6 moles of sulfonic acid group are used as anions to balance the partially oxidized polypyrrole. This results in 42% of the sulfonic acid remaining as an acid in the solid. It should be understood that ammonium cations could be completely removed with additional treatment with a proton exchange resin.

The pH-2,3-PPy / Nafion ^® was made in 1303 to light emitting devices using lumination Green was by the procedure given in Comparative Example 1 and Example 1 are followed. The thickness of PPy / Nafion ^® films, baked first at 130 ° C in air for 10 minutes and then at 200 ° C for 10 minutes in nitrogen, was 47 nm. The thickness of lumination Green 1303 baked at 130 ° C in A drying oven for 30 minutes was 60 nm. A cathode consisting of 3 nm of Ba and 240 nm of Al was thermally evaporated at a pressure of less than 4 × 10 ^-6 Torr. Encapsulation of the devices was accomplished by adhering a glass slide to the back of the devices using a UV-curable epoxy resin. Data of the device of this example, summarized in Table 1, show that PPy / Nafion ^® at pH 2.3 provides a much higher efficiency of the Luminance-Green-1303 device as Baytron-P at all pH levels. The T-50 lifetime (luminance drops to one half of the original brightness of 2600 nits) is shown in Table 1. Table 1 also shows that unlike Baytron-P PPy / Nafion ^® containing sodium or ammonium cations, at high pH has a higher efficiency of the device.

EXAMPLE 5

This example illustrates cation composition and device performance of the PPy / Nafion ^®, prepared in Example 4, but adjusted with an aqueous NaOH solution to pH 6.4.

The PPy / Nafion ^® dispersion prepared in Example 4, containing 3.88% solids and has a pH of 2.3. To about 200 ml of the dispersion was added a 1N sodium hydroxide-water solution until the pH reached 6.4. The dispersion was measured to contain 3.86% solids. 130 ° C baked films spin coated from the 6.4 pH dispersion have a conductivity of 1.7 x 10 ^-3 S / cm at room temperature. Ion chromatography analysis shows that the dispersion contains 511.8 x 10 ^-6 g Na ⁺ and 76.6 x 10 ^-6 g NH ₄ ⁺ per one ml dispersion. The ion concentration is approximately equivalent to 22.3 × 10 ^-6 mol Na ⁺ and 4.2 × 10 ^-6 mol NH ₄ ⁺ per one gram of the dispersion, or a total of 27 × 10 ^-6 mol total cation (Na ⁺ and NH ₄ ⁺ ) at a pH of 6.4. Thus, the cation concentration was 7 × 10 ^-4 moles of total cation (mainly Na ⁺⁾ per gram of solids (total of PPy plus Nafion ^®). Based on the solids% and the amount of Nafion ^®, which are used in the polymerization, the dispersion contains about 36.2 x 10 ^-6 moles of sulfonic acid group per one gram of the dispersion. This reveals that about 73% of the sulfonic acid groups in the solid form sodium and ammonium salts. Some of the remaining sulfonic anions form complexes with partially oxidized polypyrrole to balance the positive charges. It is reasonably estimated that an approximately 3.5 PPy unit is a deficient electron. The total number of PPy used in the polymerization is 36.2 x 10 ^-6 moles per gram of the dispersion. It is therefore estimated that 10.3 x 10 ^-6 moles of sulfonic acid are used as anions to balance the partially oxidized polypyrrole. This results in about 0% of the sulfonic acid being acid in the solid remain.

The pH-6.4-PPy / Nafion ^®, containing mainly sodium cations was made in 1303 to light emitting devices using lumination Green was by the procedure given in Comparative Example 1 and Example 1 are followed. Data of the device, summarized in Table 1, show that the PPy / Nafion ^®, adjusted with sodium cations of the low pH to high pH, also at low luminance rises too high efficiency. It also provides a Luminance Green 1303 device with much higher potency than Baytron-P at all pH levels. The T-50 lifetime (luminance drops to one half of the original brightness of 2900 nits) is shown in Table 1. Table 1 also shows that, unlike Baytron-P, PPy / Nafion ^® containing sodium or ammonium cations, at high pH has a higher efficiency of the device.

EXAMPLE 6

This example illustrates cation composition and device performance of the polypyrrole / Nafion ^® manufactured in Example 1 but adjusted with an aqueous NH ₄ OH solution to pH 6.4.

The PPy / Nafion ^® dispersion prepared in Example 3 containing 3.88% solids and has a pH of 2.3. About 200 ml of the dispersion was added with a 1N ammonium hydroxide-water solution until the pH reached 6.4. The dispersion was measured to contain 3.81% solids. 130 ° C baked films obtained from the 6.4 pH dispersion have a conductivity of 1.6 x 10 ^-3 S / cm at room temperature. Ion chromatography analysis shows that the dispersion contains 447.8 x 10 ^-6 g of NH ₄ ⁺ per one ml of dispersion. The ion concentration is approximately equivalent to 24.8 x 10 ^-6 moles NH ₄ ⁺ per one gram of the dispersion at pH = 6.4. Thus, the cation concentration was 6.4 × 10 ^-4 mol NH ₄ ⁺ per gram of solids (total of PPy plus Nafion ^®). Based on the solids% and the amount of Nafion ^® used in the polymerization, the dispersion contains about 35.7 x 10 ^-6 moles of sulfonic acid group per one gram of the dispersion. This reveals that about 69.5% of the sulfonic acid groups in the solid form ammonium salt. Some of the remaining sulfonic anions form complexes with partially oxidized polypyrrole to balance the positive charges. It is reasonably estimated that an approximately 3.5 pyrrole unit is a deficient electron. The total number of pyrrole used in the polymerization is 35.7 x 10 ^-6 moles per gram of the dispersion. It is therefore estimated that 10.2 x 10 ^-6 moles of sulfonic acid group are used as anions to balance the partially oxidized polypyrrole. This causes about 0% of the sulfonic acid to remain in the solid as an acid.

The pH-6.4-PPy / Nafion ^® containing ammonium cations was generated using lumination Green 1303 to emitting light by means of the procedure was given in Comparative Example 1 and Example 1 are followed. Data of the device, summarized in Table 1, show that the PPy / Nafion ^®, adjusted with ammonium cations from the low pH to high pH, also at low luminance rises too high efficiency. It also provides a Luminance Green 1303 device with much higher potency than Baytron-P at all pH levels. The T-50 lifetime (luminance drops to one half of the original brightness of 3350 nits) is shown in Table 1. Table 1 also shows that unlike Baytron-P PPy / Nafion ^® containing sodium or ammonium cations, at high pH has a higher efficiency of the device. TABLE 1 CATION COMPOSITION AND OPERATING BEHAVIOR OF THE DEVICE sample Effectiveness (Cd / A) T-50 (h) @ RT & 30 mA / cm ² @ 200 Nits @ 500 Nits @ 1000 Nits @ 2000 Nits Comp. A-1 (pH 1.7) 2.3 3.3 4.4 5.5 Comp. A-2 (pH 2.6) 2.1 3.0 4.0 5.0 Comp. A-3 (pH 3.9) 1.5 2.2 3.1 3.9 Ex. 1, PEDOT / Nafion ^® (pH 1.9, NH ₄ ⁺⁾ 13.5 14.8 15.5 16.0 110 (initial 5050 Nits) Ex. 2 PEDOT / Nafion ^® (pH 6.4, Na ⁺⁾ 15.3 14.9 14.3 14.1 240 (initial 44200 Nits) Ex. 3 PEDOT / Nafion ^® (pH 6.4, NH ₄ ⁺⁾ 12.0 13.6 14.5 15.1 74 (initial 4630 Nits) Ex. 4 PPy / Nafion ^® (pH 2.3, NH ₄ ⁺⁾ 5.3 6.5 7.7 235 (initial 2600 Nits) Ex. 5 PPy / Nafion ^® (pH 6.4, Na ⁺⁾ 7.4 8.1 9.0 385 (initial 2900 Nits) Ex. 6 PPy / Nafion ^® (pH 6.4, NH ₄ ⁺⁾ 6.4 8.2 9.7 104 (initial 3350 Nits)

you Note that not all of the above in the general Description or the activities described in the examples It requires that a portion of a specific activity may not be necessary, and that one or more additional activities in addition to those described can be performed. Still is the order in which the activities are listed are not necessarily the order in which they are performed become.

In In the foregoing description, the concepts are with reference been described on specific embodiments. however recognizes the expert that various modifications and changes can be made without from the scope of the invention as in the following claims indicated to deviate. Accordingly, the description and the figures in an illustrative rather than in a limiting sense Sense to look at and all such modifications are within within the scope of the invention.

It It should be recognized that certain characteristics of clarity because of here in the context of separate embodiments also in combination in a single embodiment can be provided. Conversely, you can various characteristics which, for the sake of brevity, in which Context of a single embodiment are described, also provided separately or in any subcombination become. Further, reference is made to the values stated in areas, every single value within that area.

SUMMARY

An electrically conductive polymer composition is provided. The composition contains an electrically conductive polymer and a fully fluorinated acid polymer having acidic anion groups. A first portion of the acidic anion groups is complexed with the electrically conductive polymer. A second portion of the acidic anion groups is in the form of a salt with cations, which may be inorganic cations, organic cations, or combinations thereof. The cation concentration is in the range of 5 x 10 ^-5 to 0.2 moles of cation per gram of solids where the solids are primarily the total of the electrically conductive polymer plus the fully fluorinated acidic polymer.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (7)

An electrically conductive polymer composition comprising an electrically conductive polymer and a fully fluorinated acid polymer having acidic anion groups, wherein a first portion of the acidic anion groups is complexed with the electrically conductive polymer and a second portion of the acidic anionic groups in the form of a salt with cations selected from inorganic cations , organic cations and combinations thereof, wherein the cation concentration is in the range of 5 x 10 ^-5 to 0.2 moles of cation per gram of solids, the solids consisting essentially of the total of the electrically conductive polymer plus the fully fluorinated acidic polymer , Conductive composition according to claim 1, wherein the conductive polymer is selected from at least one monomer from the group consisting of thiophenes, selenophenes, tellurophenes, Pyrroles and thienothiophenes, is generated. Conductive composition according to claim 1, wherein the fully fluorinated acid polymer is acidic groups from the group consisting of sulfonic acid and sulfonamide, includes. Conductive composition according to claim 1, wherein the fully fluorinated acid polymer is a perfluorinated olefin backbone with pendant perfluorinated alkylsulfonate, perfluorinated Ethersulfonat-, perfluorinated ester sulfonate or perfluorinated Ether sulfonimide groups. Conductive polymer composition according to claim 1, wherein the cations are selected from the group consisting of ammonium ions, Alkylammonium ions, sodium ions, potassium ions and combinations thereof are selected. An aqueous dispersion comprising an electrically conductive polymer and a fully fluorinated acid polymer having acidic anion groups, wherein a first portion of the acidic anion groups is complexed with the electrically conductive polymer and a second portion of the acidic anionic groups in the form of a salt with cations selected from inorganic cations, organic cations and combinations thereof, wherein the cation concentration is in the range of 5 x 10 ^-5 to 0.2 moles of cation per gram of solids, the solids consisting essentially of the total of the electrically conductive polymer plus the fully fluorinated acidic polymer. An electronic device comprising in sequence an anode, a buffer layer, a photoactive layer and a cathode, the buffer layer comprising an electrically conductive polymer and a fully fluorinated acid polymer having acidic anion groups, wherein a first portion of the acidic anion groups is complexed with the electrically conductive polymer and a second portion of the acid anion groups in the form of a salt with cations selected from inorganic cations, organic cations, and combinations thereof, wherein the cation concentration is in the range of 5 x 10 ^-5 to 0.2 moles of cation per gram of solids wherein the solids consist essentially of the total of the electrically conductive polymer plus the fully fluorinated acid polymer.